Uranium(iv) terminal hydrosulfido and sulfido complexes: insights into the nature of the uranium–sulfur bond†,10.1039/C6SC00677A

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Lactoyl-CoA 全氟丁基戊烷白叶藤碱全氟己基辛烷新白叶藤碱壳寡糖特色专题-生物多肽

Uranium(iv) terminal hydrosulfido and sulfido complexes: insights into the nature of the uranium–sulfur bond†

Michael W. Rosenzweig,Andreas Scheurer,Carlos A. Lamsfus,Frank W. Heinemann,Laurent Maron,Julie Andrez,Marinella Mazzanti,Karsten Meyer

Chemical Science Pub Date : 05/10/2016 00:00:00 , DOI:10.1039/C6SC00677A

Abstract

Herein, we report the synthesis and characterization of a series of terminal uranium(IV) hydrosulfido and sulfido complexes, supported by the hexadentate, tacn-based ligand framework (^Ad,MeArO)₃tacn³⁻ (= trianion of 1,4,7-tris(3-(1-adamantyl)-5-methyl-2-hydroxybenzyl)-1,4,7-triazacyclononane). The hydrosulfido complex [((^Ad,MeArO)₃tacn)U–SH] (2) is obtained from the reaction of H₂S with the uranium(III) starting material [((^Ad,MeArO)₃tacn)U] (1) in THF. Subsequent deprotonation with potassium bis(trimethylsilyl)amide yields the mononuclear uranium(IV) sulfido species in good yields. With the aid of dibenzo-18-crown-6 and 2.2.2-cryptand, it was possible to isolate a terminal sulfido species, capped by the potassium counter ion, and a “free” terminal sulfido species with a well separated cation/anion pair. Spectroscopic and computational analyses provided insights into the nature of the uranium–sulfur bond in these complexes.